History

The discovery of fireworks, or namely the formulation of gunpowder is believed to have occurred by chance approximately 2,000 years ago in China. It is thought that a Chinese cook accidentally mixed three common kitchen ingredients:

KNO3 (see left) Sulfur Charcoal

These were heated over a fire and dried to give a black flaky powder which burned with a loud bang when ignited. This crude, early mixture has come to be known in our modern world today as gun powder. The Chinese named this fascinating black powder "huo yao" ("Fire Chemical") and developed it further. The mixture was inserted into the hollow of a bamboo stick and when thrown into a fire, the gases produced by the ignited burning powder inside caused an immense build up of pre ssure and blasted the tube apart. The basic fire cracker was born. Thereafter, fire crackers played an essential part to Chinese festivities -weddings, religious rituals -nay cause for celebration heard their bang due to the belief that they were thought to be powerful enough to scare off evil spirits. It was inevitable that the time would come when people would begin to realise that these now powerful explosives could be applied to warfare. The Chinese were well aware of the killing power these explosives had and within 100 years had not only developed fire arrows (bamboo fire crackers attached to regular arrows and shot at the enemy) but even 'Ground Rats'. These consisted of propelling rats from inside the bamboo fire crackers and toward the enemy, creati ng a great psychological effect -scaring soldiers and causing horses to go wild.

Before long, the knowledge of fireworks began to spread to the west. It is believed that Marco Polo on one of his many trips to China transported this invention to the Middle East where European Crusaders brought it to England. An English Scholar by the name of Roger Bacon (1214 -1294) was one of the first Europeans to study gunpowder and write about it. He wrote "..... if you light it you will get thunder and lightening if you know the trick......." and realised that it was the Salt Peter (KNO3) that was the driving

force behind the explosion. On the contrary, he knew his findings had the dangerous potential of completely revolutionising warfare. Therefore, he wrote his finding s in code in the hope to save lives in case information reached the hands of the wrong people. This code was not deciphered for hundreds of years. It was in 1560 that European Chemists managed to make gunpowder as explosive as possible by experimenting wit h the ratios of the ingredients. The final proportion was set as follows: 1) Salt Peter 75% 2) Charcoal 15% 3) Sulphur 10% These ratios are still used today some 500 years later. This brought the end of medieval warfare causing it to come to a close as me tal armour could now be punctured by bullets and once seemingly impenetrable walls of castles could be blown to bits by cannon balls. Credit for developing fireworks into a true art form has to be awarded to the Italians. It was they who were able to devel op aerial shells that launched upward and exploded into a fountain of colour; lighting up the night sky to the enjoyment of onlookers.

These firework displays grew more and more elaborate over the years, gradually working their way into the back gardens of everyday families. For nearly 2,000 years, the only colours fireworks could produce were yellows and oranges using steel and charcoal. It was only in the 19th Century that pyrotechnicians had the technology to introduce reds, greens and blues to the night sky. However the field of pyrotechnics is far from fulfilled. There are problems that have been stumbled across that are yet to be solved (for example the production of forest green coloured fireworks) and certain areas of the field have not yet even been touched upon or explored. The field of pyrotechnics has both an exciting history and future and its development continues to this day.

Composition
The Chemistry of fireworks is based on the simple theory of combustion. The composition inside the firework must however contain 6 vital ingredients:

Fuel
Charcoal, commonly known in the pyrotechnic industry as black powder is the most common fuel used in fireworks. Normally, all fuels will contain an organic element such as charcoal or thermite. The mechanism by which the fuel functions in the firework is relatively simple. The fuel loses electrons to atoms within the oxidiser (thereby reducing the oxidiser) and releasing atoms from the oxidiser. During this process, bonds are formed between the fuel and oxygen atoms forming a product which is relatively stable. However, only a minimal amount of energy is required to start the combustion of this fuel oxidiser compound. When combustion does start, the result is a massive release of energy as the solid mixture liquefies and vaporises into the flame of ignition. This maximises the probability of reaction of the oxidiser as it is brought into the close proximity of the flame.

Oxidising Agents
The function of the oxidising agent is to produce the oxygen nee ded in order for the mixture inside the firework to burn. These oxidisers can be nitrates, chlorates or perchlorates.

Nitrates only give up a third of their oxygen as the equation above illustrates. On the contrary, Chlorates get completely reduced as th ey are better oxidising agents and so cause an even more spectacular reaction. This however does cause the reaction to become extremely explosive.

Perchlorates contain even more oxygen but are less likely to explode than chlorates due to their increase i n stability. They follow the reaction below:

Reducing Agents
The second part to a firework is the reducing agent. These burn the oxygen provided by the oxidising agents to produce hot gasses. Common reducing agents are Sulphur and Charcoal. These react w ith the oxygen to form Sulphur dioxide and Carbon dioxide respectively as illustrated below.

By mixing both the reducing agents, the speed of the reaction can be controlled.

Regulators
Metals can be added to regulate the speed at which the reaction. The larger the surface area of the metal, the faster the reaction will proceed (collision theory).

Colouring Agents
Different chemicals are used to produce different coloured fireworks. Therefore, in order to produce a firework of a certain colour, the correct corresponding chemical or as the case may be, mixture of chemicals can be used: Metal Colour

Strontium

Red

Copper

Blue

Barium

Green

Sodium

Yellow/Orange

Calcium

Orange

Gold

Iron

Hence Strontium used in conjunction with Copper will yield a purple firework. The incandescence from the elements occurs when solid particles are heated in the flame to extremely high temperatures. These release excess energy in the form of light (hv) at the broad end of the spectrum. The higher the temperature, the shorte r the wavelength at which light is emitted, and the nearer it tends toward the blue end of the coloured spectrum. This is why blue coloured fireworks are so hard to synthesise, as they only occur at very high temperatures.

Binders
Binders are used to hold what is essentially the mixture of the firework together in a paste like mixture. The most commonly used binder is known as dextrin, a type of starch which holds the composition together. Paron can also be used in binding, however it is less common and only used in conjunction with red and green fireworks as it helps to enhance their colour.

The binders do not actually begin to work until the firework has been lit as they are too unstable for storage within the firework and are henc e potentially dangerous.

Light and Colour

Fireworks have lit up the night sky for centuries however, colour is an invention that has only been introduced into displays in the last 100 years. Before the 19th Century, the only colours that coul d be produced were yellows and oranges with the use of steel and charcoal. Later development involved Chlorates which introduced basic reds and greens to the repertoire. Good blues and purples were not developed until this century and the quest for the for mation of a deep forest green coloured firework continues still to this day. Colour production in fireworks involves two main mechanisms: 1) Incandesence 2) Luminescence Incandescence is the light produced from heat. Heat causes a substance to grow hot and glow. This results in the emission of infrared, then red, orange, yellow, and white light as the substance grows increasingly hotter. The power of this emission can be defined as: M = sT4 Where s is the Stefan-Boltzmann constant and T is the temperature. It is apparent from the equation that a twofold increase in emission can be caused by increasing the flame temperature from 400K to 800K. The calculated emission spectrum has the following shape:

The graph illustrates that different temperatures produces a different wavenumber with a different power of emission and so produce a different colour of light. The following table gives a summary of the temperatures at which various colours will occur. Temperature (K) Temperature (0C) Subjective Colour

750

480

Faint red glow

850

580

Dark red

1000

730

Bright red/orange

1200

930

Bright orange

1400

1100

Pale orange/yellow

1600

1300

Yellow/white

>1700

>1400

White

Blues and greens require much higher temperatures (ones which are impractical for fireworks) and so cannot be formed using this method. Instead, they are created via the mechanism of Luminescence. Luminescence is light produced using energy sources other than heat. This involves the absorption of energy by an electron of an atom or molecule thereby ca using it to become excited but also unstable. As the electron drops back down to its ground state, energy is released and in this case, it is in the form of light as the energy is released in the form of a phonon. The energy of the phonon determines its wavelength and colour. Certain molecules emit light in the visible region and these are used to produce the colours seen in fireworks. Some of these however need to be combined with another element to stabi lise them and make them fit for use within firework s. For example, Barium must be combined with chlorinated rubber as it is unstable at room temperature. On the contrary, Copper Chloride is instable at high temperatures and it must be ensured that the firework does not get too hot.

The following table illu strates the compounds required to produce specific coloured fireworks. Wavelength of Light

Colour

Compound

Red

Strontium Salts & Lithium Salts Li2CO3 SrCO3

600-646nm

Orange

Calcium Salts CaCl2 CaSO4.2H2O

591-603nm

Gold

Incandescence of Iron or Charcoal

590nm

Yellow

Sodium Compounds NaNO3 Na3AlF6

589nm

Electric White

White Hot Metal BaO

564-576nm

Green

Barium compounds with Chlorine BaCl+

511-533nm

Blue

Copper Compounds and Chlorine Cu3As2O3Cu(C2H3O2)2

460-530nm

Purple

Mixture of Strontium (red) and Copper (blue) compounds

432-456nm

Silver

Burning aluminium, titanium or magnesium powder.

412nm

In order to choose the colours of fireworks which are most pleasing to the eye, pyrotechnicians use a Chromacity Diagram as illustrated below:

This is designed using the three primary colours red, yellow and blue. In theory, if fireworks of these colours can be produced then the production of a firework of any colour is possible. The wavelength at which every colour lies can be found on the curved line surrounding the tongue shaped region of the composite colours. The numbers along the curve represent corresponding wavelengths in nanometres. Unfortunately, the case is not as simple as selecting a colour and finding the corresponding wavelength. Some emitt ing molecules are so reactive that they cannot be directly packed into a firework. Therefore, the relevant molecules must be evaporated into the flame to keep them at as high a temperature as possible. To achieve maximum light output substantial amounts of emitters must be present in the flame alongside 5 other vital ingredients. It has taken pyrotechnicians years to solve the problems which lie behind coloured flame production. Success has been attained in all areas save for the production of the much sought after ocean and forest green coloured firework.

A combination of green and blue coloured emmiters (such as BaCl and CuCl) is the obvious choice however BaCl emission is very rare as they occur as BaOH and BaO emissions which fall in the yellow -green section of the spectrum. Hence the quest for the forest and ocean green coloured fireworks still continues.

Construction
The practical aspect to fireworks is just a s important as the theory calculations regarding the temperature and wavele ngths at which certain fireworks occur are useless to pyrotechnicians unless the knowledge can be put into practice.

Sights such as the that pictured above originate from small shells. They are reliant on lift charge in order to propel the shell into the air. This process is kick started by use of a time fuse which leads up to the shell causing it to explode. The energy from this propels the shell containing black powder and star pellets from the launch tube into the air. Attached to this is a Time delay fuse which is the source of the final explosion where the stars are released into the sky. Click on the interactive image below for more detail on the construction of fireworks.

Lift Charge
The original fuse that is lit from the ground causes the combustion of black powder (Potassium Nitrate, Sulphur and Charcoal) within a confined space hence resulting in a huge explosion due to a massive increase in heat and gas within the shell. The strength of this explosion can hurtle the firework as high as 1 000 feet into the air.

Health & Safety

The number of injuries caused by fireworks each year is relatively low and accidents are now many fewer than in previous years. However, care and precaution must always be taken when using fireworks to ensure safety. Under no circumstances should unlicensed people attempt to synthesise fireworks. This website has been formed to illustrate the Chemistry behind fireworks, not as a guideline as to how they should be made. Safety guidelines can be found here

References
Beilstein Chemdraw The Chemistry of Fireworks, Royal Society of Chemistry, Michael S. Russell, 1st edition, 2000